CN1322023C - Modified polyester - Google Patents
Modified polyester Download PDFInfo
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- CN1322023C CN1322023C CNB2005100775650A CN200510077565A CN1322023C CN 1322023 C CN1322023 C CN 1322023C CN B2005100775650 A CNB2005100775650 A CN B2005100775650A CN 200510077565 A CN200510077565 A CN 200510077565A CN 1322023 C CN1322023 C CN 1322023C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A polyester which has ethylene terephthalate units as main repeating units, is made up of monomer units wherein the acid units contain 2.0 to 3.0 mol% isophthalic acid units having a metal sulfonate group, and contains 9.0 to 13.0 wt.% polyalkylene glycol having an average molecular weight of 1,000 to 10,000 in the polymer, characterized in that the content of DEG units in all the glycol units is 4.7 to 5.7 mol% and that the ratio of the maximum of intrinsic viscosity, [ eta ]max, to the minimum thereof, [ eta ]min, is from 1.0 to 1.02. The modified polyester is reduced in viscosity decrease and coloration during melt spinning while retaining sufficient solubility in aqueous alkali solutions. It is excellent in spinnability and productivity.
Description
This case is
February 15 calendar year 2001, application number is
01801648.0,
Denomination of invention is
Modified poly ester and method for continuous production thereofDivide an application
Technical field
The present invention relates to as easy as rolling off a log dissolved modified poly ester of buck and method for continuous production thereof.Be particularly related to that limiting viscosity is stable, the easy dissolved polyester of alkali of spinning operation and silk stable physical property, and can the efficient height, the directly continuously poly-manufacture method of the easy dissolved polyester of alkali that production cost is low.
Background technology
The easy dissolved polyester of alkali is used the constituent that another composition B is divided into the Splittable conjugate fiber of a plurality of forms as having a composition A.With regard to conjugated fibre, for example disclosed in public clear 63-20939 communique of spy and special fair 8-14042 communique, it is to be dissolved out by at least a portion that alkaline purification will be cut apart composition, as cutting apart silk, the conjugated fibre made from the purpose of the extra fine filament that obtains superfine fiber number, this conjugated fibre are used to make the high-density cloth with well-pressed style or have the graceful gloss and the thin,tough silk class cloth of soft feel.
And conjugated fibre is used as the polyester cloth and silk that is fit to so-called bleaching processing, the constituent of for example opening the cloth and silk of putting down in writing in the flat 4-91894 communique the spy.
Past, the easy dissolved polyester of alkali various researchs have been carried out, for example in the public clear 47-47532 communique of spy, proposed to add the polyethylene terephthalate of the polyalkylene glycols of 5～16 weight %, and, in the public clear 63-20939 communique of spy, proposed will with the polyethylene terephthalate of 3 moles of 5-sodium sulfonate group-isophthalic acid ester copolymerization more than the %.
But, with regard to the former situation,, will produce the thermotolerance of polymkeric substance, the deterioration of anti-atmospheric oxygen voltinism, the viscosity degradation when dissolving spinning, painted, as to twist operation problems such as efflorescence if the containing ratio of polyalkylene glycols is more.And, situation with regard to the latter, if the copolymerization rate of 5-sodium sulfonate group-isophthalic acid ester is more, just existence is held cohesion, the gelation tackify that electric charge causes because of 5-sodium sulfonate group-isophthalic acid ester, and make difficulty in spinning, and the spinning filtration pressure is sharply risen because of producing fine gel, the shortcoming of spinning operation deterioration.
So the scheme that has re-used after having proposed two kinds of compositions to be suited adjust in public clear 61-1551 communique of spy and the flat 1-162825 communique of Te Kai can not solve fully but present situation is the problems referred to above.
Now, the main flow of making the method for modified poly ester is the ester-interchange method (hereinafter referred to as the DMT method) that the spy opens the use dimethyl terephthalate (DMT) of putting down in writing in the clear 62-89725 communique, in the DMT method, generally is batch process.And, on the books as the manufacture method that relates to the direct polymerization method (hereinafter referred to as straight poly-method) of using terephthalic acid at the public clear 58-45971 communique of spy, but this also is a batch process.If use batch process, will there be following problem: because polymer-extruded timeliness changes, polymer viscosity when generation begins to extrude with extrude the different of polymer viscosity when finishing, and, if increase lot number, remaining polymkeric substance is sneaked into the deterioration foreign matter in the still, increases the difference of the polymer physics performance between each batch.For the countermeasure of improving these problems reduces lot number exactly, the blending polymer beads, but production efficiency is low, can not produce cheaply.
As above-mentioned countermeasure, for example opening the spy has proposed to use direct continuous polymerization, esterification to finish back extraction oligopolymer, import the method made from the batchwise polymerization method in the other polymerization tank in the clear 62-146921 communique, but because of polyreaction becomes batch mode, also have polymer physics performance inequality, can not satisfy the demand, the equipment complicated problems.
Summary of the invention
In order to solve the shortcoming of prior art, the object of the present invention is to provide a kind of have sufficient buck solvability and when dissolving spinning viscosity reduce and painted less, textile operation is good, production performance is good modified poly ester.
In order to achieve the above object, the invention provides a kind of main repeating unit is ethylene glycol terephthalate, the m-phthalic acid composition that contains the metal organic sulfonate base that in sour composition, contains 2.0～3.0 moles of %, the molecular-weight average that contains 9.0～13.0 weight % in polymkeric substance is the polyester of 1000～10000 polyalkylene glycol, it is characterized in that: in glycol component, the molar percentage of contained DEG is 4.7～5.7 moles of %, and the ratio of the maximum value of limiting viscosity [η] max and minimum value [η] min is: 1.0≤[η] max/[η] min≤1.02.
And, the manufacture method of polyester of the present invention is characterised in that: with terephthalic acid, ethylene glycol, the m-phthalic acid composition that contains the metal organic sulfonate base, polyalkylene glycol is a raw material, carry out the direct esterification reaction, condensation reaction and when making polyester, make dicarboxylic acid composition and ethylene glycol slurryization, adjusting PH is 4.5～5.5, be under 1.1～1.2 the condition in total mol ratio, make this slurry carry out the successive esterification, in the oligopolymer that is generated, add after the polyalkylene glycol, import polymerization tank successively, that carries out polyreaction etc. under reduced pressure carries out a series of reaction continuously.
The easily-soluble modified polyester of alkali of the present invention is because very fast for the dissolution rate of basic solvent, under condition near common polyethylene terephthalate, operability is good, can dissolve spinning, aftertreatment, thus can efficient be used in goodly the extra fine filament manufacturing with conjugated fibre and bleaching processing with in the manufacturing of cloth and silk.
Description of drawings
Fig. 1 is an expression step of manufacturing synoptic diagram of the present invention.
Nomenclature: 1 slurry groove; 2 the 1st esterification grooves; 3 the 2nd esterification grooves; 4 polymerization tanks; Input ports such as a, b properties-correcting agent.
Embodiment
Describe the present invention below in detail.The compound (hereinafter referred to as SIPE) that the m-phthalic acid composition that contains the metal organic sulfonate base that uses in the present invention adopts 5-sulfonic acid metal matrix-dimethyl isophthalate (hereinafter referred to as SIPM) or spent glycol and dimethyl ester to carry out transesterify.If the SIPM that drops into is excessive, will make the slurry physical deterioration, so preferably adopt SIPE in slurry tank.Metal among SIPM or the SIPE can use sodium, potassium, lithium etc., but sodium most preferably.
The copolymerization rate of SIPE need be set at 2.0～3.0 moles of % in the sour composition of polymkeric substance.If the copolymerization rate of SIPE is lacked than this, just can not obtain sufficient alkali dissolution.On the other hand, if the copolymerization rate is more than this, will produce tackify, gelation because of the charge effect that dissolves the SIPE in the spinning process, operability significantly descends.
And polyalkylene glycol can be used general expression HO (C
nH
2nO)
mH (wherein n, m are positive integer) expression, the polyoxyethylene glycol during n=2 (hereinafter referred to as PEG) is to be widely used and is optimal.
The molecular weight of PEG used in the present invention need be 1000～10000.If molecular weight less than 1000 will cause the hydrolysis reaction of modified poly ester easily when dissolving spinning, the thermotolerance of polyester is insufficient, sticks together between polyester granulate, in twisting operation generation efflorescence.And, if molecular weight surpasses 10000, will lack polymerisation reactivity, because be difficult to PEG is copolymerized in the molecular chain of polyester, so the scale resistance of polyester worsens.
The copolymerization amount of PEG need be 9.0～13.0 weight % of polymkeric substance.If copolymerization quantity not sufficient 9.0 weight %, the buck solubility property is just insufficient, and on the other hand, if surpass 13.0 weight %, the thermotolerance of polymkeric substance, scale resistance just worsen.
The maximum value of the limiting viscosity of polyester of the present invention [η]
MaxAnd minimum value [η]
MinRatio be: 1.0≤[η]
Max/ [η]
Min≤ 1.02.[if η]
Max/ [η]
MinOutside above-mentioned scope, when spinning, will often break, shorten the life-span of spinning mould mouth etc. because of the deterioration of spinning filterableness, operability worsens.
And,, in glycol component, contain the glycol ether (DEG) of 4.7～5.7 moles of % with regard to polyester of the present invention.This DEG generates because of the side reaction in the polymerization.If 4.7 moles of % of less than, the buck solubility property just worsens.And if surpass 5.7 moles of %, the thermotolerance of polymkeric substance, scale resistance just worsen, and the operability when dissolving spinning significantly worsens.
Describe the manufacture method of the modified poly ester of claim 2 of the present invention below in detail with accompanying drawing.
(Fig. 1) be the step synoptic diagram of expression one embodiment of the present of invention.In slurry groove 1,, contain the m-phthalic acid compound of metal organic sulfonate base and make it slurryization from input port a input to 1 with after terephthalic acid and the ethylene glycol slurryization.Then, this slurry is supplied to continuously in the 1st esterification groove 2 and carry out esterification and form oligopolymer.And the oligopolymer that generates supplied in the 2nd esterification groove 3 successively, add polyalkylene glycol at input port b.Then, this oligopolymer is supplied in the polymerization tank 4 successively continuously, and under vacuum state, carry out polyreaction continuously to the given polymerization degree.To reach the polymer-extruded to cooling bath of the given polymerization degree from the polymkeric substance relief outlet (not shown) of polymerization tank 4 by pore, the bar of extruding be carried out granulation by cutting device.
At this, it is important the m-phthalic acid composition that contains the metal organic sulfonate base being added to equably in the slurry of prior synthetic terephthalic acid and ethylene glycol.With regard to existing technological thought, in order to suppress generally to be SIPE is put in the low oligopolymer of acid number because of SIPE has the caused gel of electric charge.But, have viscosity height, so the dispersiveness of SIPE worsens, produces the problem of cohesion because of the oligopolymer of esterification end.And, put into ethylene glycol in the oligopolymer that esterification finishes and the depolymerization that reduces the polymerization degree only is applicable to batch-wise manufacture method.As the present invention, by SIPE being dropped into equably and is distributed in the slurry of terephthalic acid and ethylene glycol, can address the above problem, can adopt the good continuous polymerization method of efficient.
Like this, also need in modulated slurry, to add the oxyhydroxide of such basic metal such as oxyhydroxide, acetate, the carbonate of sodium, potassium, lithium, magnesium, calcium etc. or alkaline-earth metal and salt of weak acid etc., the pH value of slurry is adjusted in 4.5～5.5 the scope.Specifically, be used to modulate pH value and the compound that adds can be enumerated sodium acetate, potassium acetate, lithium acetate, sodium hydroxide, potassium hydroxide etc., but sodium acetate, lithium acetate etc. are handy especially.Add these compounds and be not limited to special method, but the addition means that for example it is dissolved in a spot of ethylene glycol suits.
If the pH value less than 4.5 of slurry, the side reaction of DEG is just extremely many.On the other hand, if pH value surpasses 5.5, the color of polymkeric substance increases the weight of, and produces a lot of insolubless in polymkeric substance, so can not get being fit to practical polymkeric substance.PH value is preferably in 4.7～5.3 scope.
In the present invention, the total mol ratio in the time of need be with esterification is set at 1.1～1.2.If this mol ratio surpasses 1.2, will generate the physicals of DEG, infringement polymkeric substance in a large number.And, if less than 1.1 because the amount of ethylene glycol is insufficient, just can not normally be carried out esterification, polyreaction.
The b that the input of PEG is preferably in Fig. 1 carries out, and carries out at the 1st esterification groove 2.The standard that drops into is that the esterification yield of oligopolymer is more than 80%.If esterification yield is more than 80%, even because of the input of PEG produces boiling phenomenon, but because the amount of free ethylene glycol seldom, so can suppress intrasystem foamed phenomenon.
As the purpose of improving various physicalies, can in polyester of the present invention, add photostabilizer, heat-resistant agent, matting agent etc.The input of these additives can be carried out in any operation in manufacturing process.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.In addition, measure the characteristic value of the following examples by method shown below.
(1) limiting viscosity [η]
The sample collecting that the limiting viscosity of polymerization grain [η] is measured usefulness is performed as follows.With regard to the polymkeric substance that uses continuous polymerization to produce, with reasonable time gather the polymerization grain at interval and with it as sample, with regard to the polymkeric substance that uses the batch-type polymerization to produce, begin to extrude and extrude the polymerization grain of firm end for each batch polymerization thing, and in extruding the way, gather suitable polymerization grain and with it as sample.In the mixed solvent of phenol/tetrachloroethane=6/4 (weight ratio), under 20 ℃ of conditions, by crow uncle class moral method working sample.In addition, sample number is 5, in 5 samples, with the limiting viscosity of maximum as [η]
Max, with the limiting viscosity of minimum as [η]
Min, calculate [η] by measurement result respectively
Max/ [η]
Min, and as the index of the limiting viscosity inequality of polymkeric substance.
(2) glycol ether (DEG) amount
With regard to the glycol ether amount, after the polyester granulate pulverizing, alkalize with potassium hydroxide-methanol solution, after the pure water hydrolysis, after the terephthalic acid neutralizing treatment, carry out gas chromatographic analysis, try to achieve DEG content with marker method, the molar percentage of the DEG in the polymkeric substance is calculated by following formula:
DEG mole %=DEG mole number/(DEG mole number+EG mole number).
(3) spinning operation
Use this modified poly ester and common PET (polyester) to carry out the spinning of superfine Splittable conjugate fiber, from the degree that spinning filter to be risen, the fracture of wire number of times is estimated, with zero, △, * represent.
(4) thermotolerance
Above-mentioned superfine Splittable conjugate fiber is twisted processing, by the logical out of date efflorescence state of operation and not the backtwisting state estimate, with zero, △, * represent.
(5) alkali dissolution
Use above-mentionedly to add twisted filament and make tubular knitted test portion, the aqueous sodium hydroxide solution with 1% (50,98 ℃ of bath raioes) carries out the alkali dissolution test, estimate by the minimizing speed of its weight, with zero, △, * represent.
Embodiment 1
With terephthalic acid, ethylene glycol, SIPE (accounting for 2.3 moles of % in sour composition) puts in the slurry tank, to wherein adding with respect to polymkeric substance is the trimethyl phosphate of 45ppm and the sodium acetate trihydrate of 600ppm, and the pH value of adjusting slurry is 5.2, then slurry is supplied in the 1st esterification groove continuously and carry out 270 ℃, 68.6kpa compressive reaction, supply to continuously in the 2nd esterification groove, the molecular-weight average that adds 10 weight % in this oligopolymer is 8000 polyoxyethylene glycol, 0.3 the IRGANOX245 of weight % (Ciba-Geigy corporate system) as hindered phenolic oxidation inhibitor, the ANTIMONY TRIOXIDE SB 203 99.8 PCT that is dissolved in ethylene glycol of 400ppm, mol ratio in the 2nd esterification groove is set at 1.14 and carry out esterification under normal pressure, then, continuously to the initial stage polymerization tank, transmit slurry in the later stage polymerization tank, and under 280 ℃, carry out polyreaction continuously, obtain the modified poly ester polymkeric substance of (table 1) record.In addition, the residence time that finishes from the esterification to the polyreaction is 6.2 hours, and throughput rate is 35t/D.
Embodiment 2, comparative example 1～9
Except that the copolymerization amount, addition of (table 1) record, total mol ratio, carry out the polyreaction identical with embodiment 1, obtain the modified poly ester polymkeric substance of (table 1) record.On the other hand, except total mole is made as 1.09, under the condition identical, carry out polyreaction, just can not carry out polymer polymerizing and react, can not obtain the modified poly ester polymkeric substance with embodiment 1.
Then, be that 1: 3 conjugated fibre carries out spinning with 3200 meters/minute spinning speed with the ratio of this modified poly ester polymkeric substance and common polyethylene terephthalate, obtain the part orientation conjugated fibre of 128 dtexs/25 thread.Spinning operation separately is recorded in table 1.On the other hand, use this conjugated fibre under 200 meters/minute of linear speeds, 1.5 conditions that stretch, well heater is altered to 180 ℃～210 ℃ and twist, and the fluffing generation state that is caused by heater temperature carries out stable on heating evaluation, obtains the result of (table 1) record.And, with 1% aqueous sodium hydroxide solution (50,98 ℃ of bath raioes) this is added twisted filament and carry out the alkali decrement treatment, by decrement speed evaluation alkali dissolution.
As the embodiment 1 and 2 of scope of the present invention be when being suitable for spinning operation, twisting thermotolerance, alkali decrement any one.But comparative example 1～9 lacks any one of spinning operation, thermotolerance, alkali dissolution not within the scope of the invention.
Comparative example 10
Terephthalic acid, ethylene glycol, SIPE (is the 2.3%[mole with respect to sour composition]) are put in the slurry tank, to wherein adding with respect to polymkeric substance is the trimethyl phosphate of 45ppm and the sodium acetate trihydrate of 600ppm, and the pH value of adjusting slurry is 5.2, with total mol ratio is 1.0 to put in the batch-type pressurization esterifier, under 270 ℃, the pressurized conditions of 68.6kpa, carry out 2.5 hours esterification, obtain esterification yield and be 84% oligopolymer.Then, adding in this polymkeric substance with respect to polymkeric substance is that the molecular-weight average of the IRGANOX245 as hindered phenolic oxidation inhibitor (Ciba-Geigy corporate system) of 0.3 weight % and 10 weight % is 8000 polyoxyethylene glycol, and esterification is over.Then, add the ANTIMONY TRIOXIDE SB 203 99.8 PCT that is dissolved in ethylene glycol of 400ppm, the sour composition of total and the mol ratio of ethylene glycol are made as after 1.2, move on in the polymerization reactor.Temperature of reaction is risen to 280 ℃ on one side, on one side pressure is reduced to below the 0.13kpa from 101.3kpa, and kept 1 hour, under 280 ℃, carry out 2.5 hours polycondensation, obtain the modified poly ester polymkeric substance of (table 1) record.Thereafter evaluation is identical with embodiment 1.
Comparative example 11
With the SIPE of dimethyl terephthalate (DMT), 2.3 moles of %, ethylene glycol, be the sodium acetate trihydrate of 600ppm, be 1.9 to put in the batch-type esterifier with mol ratio with respect to polymkeric substance, interpolation as catalyst for ester exchange reaction, be the four hydration manganous acetates of 175ppm with respect to polymkeric substance, according to usual method, under nitrogen gas stream, normal pressure down rises to 235 ℃ with temperature from 140 ℃ while stirring, use 4 hours, finishes transesterification reaction.Then, the molecular-weight average that adds 8.0 weight % is the IRGANOX245 as hindered phenolic oxidation inhibitor (Ciba-Geigy corporate system) of 3000 polyoxyethylene glycol, 0.3 weight %, the trimethyl phosphate of 350ppm, the ANTIMONY TRIOXIDE SB 203 99.8 PCT that is dissolved in ethylene glycol of 400ppm, after mixing, be transferred in the batch-type polymerization reactor.Then, under 280 ℃ of temperature of reaction, pressure is reduced to below the 0.13kpa from 101.3kpa, and keep this state, carry out 2.5 hours polycondensation, obtain the modified poly ester of (table 1) record with 1 hour.Thereafter evaluation is identical with embodiment 1.
What comparative example 10,11 adopted is manufacture method of the present invention batch-type polymerization process in addition, has produced the problem that limiting viscosity is big, the spinning broken string is many, the spinning filtration pressure is high.
[table 1]
| Polymerization process | SIPE (mole %) | PEG (weight %/molecular weight) | Limiting viscosity mean value [η] m | [η]max/ [η]min | Sodium acetate addition (ppm) | Slurry pH | Total mol ratio | DEG (mole %) | ||
| Embodiment | 1 | Direct continuous processing | 2.3 | 10.0/8000 | 0.770 | 1.007 | 600 | 5.2 | 1.14 | 5.50 |
| 2 | Direct continuous processing | 2.3 | 10.0/3000 | 0.700 | 1.013 | 600 | 5.2 | 1.20 | 5.30 | |
| Comparative example | 1 | Direct continuous processing | 2.3 | 10.0/12000 | 0.822 | 1.014 | 600 | 5.2 | 1.14 | 5.25 |
| 2 | Direct continuous processing | 2.3 | 10.0/600 | 0.654 | 1.003 | 600 | 5.2 | 1.14 | 5.32 | |
| 3 | Direct continuous processing | 2.3 | 10.0/8000 | 0.771 | 1.009 | 600 | 5.2 | 1.22 | 6.14 | |
| 4 | Direct continuous processing | 2.3 | 10.0/8000 | 0.773 | 1.016 | 800 | 5.8 | 1.14 | 4.50 | |
| 5 | Direct continuous processing | 2.3 | 10.0/8000 | 0.782 | 1.011 | - | 4.4 | 1.14 | 7.56 | |
| 6 | Direct continuous processing | 1.8 | 12.0/3000 | 0.746 | 1.004 | 500 | 5.5 | 1.10 | 4.76 | |
| 7 | Direct continuous processing | 2.3 | 13.5/8000 | 0.840 | 1.015 | 600 | 5.2 | 1.14 | 5.47 | |
| 8 | Direct continuous processing | 3.5 | 10.0/8000 | 0.615 | 1.017 | 800 | 5.4 | 1.14 | 5.63 | |
| 9 | Direct continuous processing | 2.3 | 8.0/3000 | 0.668 | 1.008 | 600 | 5.2 | 1.14 | 5.42 | |
| 10 | Direct batch method | 2.3 | 10.0/8000 | 0.822 | 1.055 | 600 | 5.2 | 1.20 | 5.70 | |
| 11 | The DMT batch method | 2.3 | 10.0/3000 | 0.815 | 1.028 | - | - | - | 3.10 |
[table 2]
| Spinning operation | Thermotolerance | Alkali dissolution | ||
| Embodiment | 1 | ○ | ○ | ○ |
| 2 | ○ | ○ | ○ | |
| Comparative example | 1 | ○ | × | ○ |
| 2 | × | × | ○ | |
| 3 | × | × | ○ | |
| 4 | × | ○ | △ | |
| 5 | × | × | ○ | |
| 6 | ○ | ○ | × | |
| 7 | △ | × | ○ | |
| 8 | × | ○ | ○ | |
| 9 | ○ | ○ | × | |
| 10 | × | ○ | ○ | |
| 11 | × | ○ | ○ |
Claims (1)
1. polyester, it is characterized in that: its main repeating unit is an ethylene glycol terephthalate, the m-phthalic acid composition that contains the metal organic sulfonate base that in sour composition, contains 2.0～3.0 moles of %, in polymkeric substance, contain more than the 9.0 weight %, be polyalkylene glycol greater than 1000, below 10000 less than the molecular-weight average of 13.0 weight %
In glycol component, the molar percentage of contained glycol ether is 4.7～5.7 moles of %, the maximum value of the limiting viscosity of polyester [η]
MaxAnd minimum value [η]
MinRatio be: 1.0≤[η]
Max/ [η]
Min≤ 1.02.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000083791 | 2000-03-24 | ||
| JP200083791 | 2000-03-24 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018016480A Division CN1260269C (en) | 2000-03-24 | 2001-02-15 | Modified polyester and process for continuously producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1702092A CN1702092A (en) | 2005-11-30 |
| CN1322023C true CN1322023C (en) | 2007-06-20 |
Family
ID=18600367
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018016480A Expired - Lifetime CN1260269C (en) | 2000-03-24 | 2001-02-15 | Modified polyester and process for continuously producing same |
| CNB2005100775650A Expired - Lifetime CN1322023C (en) | 2000-03-24 | 2001-02-15 | Modified polyester |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018016480A Expired - Lifetime CN1260269C (en) | 2000-03-24 | 2001-02-15 | Modified polyester and process for continuously producing same |
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| Country | Link |
|---|---|
| JP (1) | JP3483871B2 (en) |
| KR (1) | KR100499718B1 (en) |
| CN (2) | CN1260269C (en) |
| AU (1) | AU2001232315A1 (en) |
| TW (1) | TW550274B (en) |
| WO (1) | WO2001070848A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4726315B2 (en) * | 2001-03-23 | 2011-07-20 | Ｋｂセーレン株式会社 | Atmospheric pressure cationic dyeable polyester and its continuous production method |
| JP2006131711A (en) * | 2004-11-04 | 2006-05-25 | Nippon Ester Co Ltd | Readily alkali-soluble polyester resin |
| KR101224789B1 (en) * | 2005-03-07 | 2013-01-21 | 케이비 세렌 가부시키가이샤 | Normal pressure cation dyeable polyester, textile product made from the same, and process for production of the same |
| JP2008115244A (en) * | 2006-11-02 | 2008-05-22 | Toyobo Co Ltd | Method for producing copolyester |
| CN101200536B (en) * | 2006-12-13 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Basic aqueous easily-soluble modified polyesters and preparation method |
| KR100841175B1 (en) * | 2007-05-02 | 2008-06-24 | 주식회사 효성 | Atmospheric cationic dye dyeable copolyester polymer, manufacturing method thereof, and atmospheric cationic dye dyeable copolyester fiber using the same |
| CN101545154B (en) * | 2009-03-26 | 2011-11-30 | 海盐金霞化纤有限公司 | Anion polyester fiber capable of being dyed at normal temperature and normal pressure, preparation method and application thereof |
| JP2013170251A (en) * | 2012-02-22 | 2013-09-02 | Teijin Ltd | Copolyester and polyester fiber |
| JP6379643B2 (en) * | 2014-05-07 | 2018-08-29 | 三菱ケミカル株式会社 | Modified polyester fiber and its mixed goods |
| CN105111423B (en) * | 2015-09-15 | 2017-07-14 | 彭春海 | A kind of polymer waterborne polyester and preparation method thereof |
| KR20190076681A (en) * | 2017-12-22 | 2019-07-02 | 서울대학교산학협력단 | Method for Preparing Polyalkylene Terephthalate glycol |
| WO2023203975A1 (en) * | 2022-04-22 | 2023-10-26 | 東洋紡エムシー株式会社 | Copolymer polyester resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5097004A (en) * | 1990-05-11 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Novel polyesters and their use in compostable products such as disposable diapers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07116282B2 (en) * | 1986-08-19 | 1995-12-13 | 東レ株式会社 | Modified polyester for fibers |
| JPH06184415A (en) * | 1992-12-18 | 1994-07-05 | Teijin Ltd | Modified polyester |
-
2001
- 2001-02-13 TW TW090103111A patent/TW550274B/en not_active IP Right Cessation
- 2001-02-15 WO PCT/JP2001/001102 patent/WO2001070848A1/en active IP Right Grant
- 2001-02-15 JP JP2001569044A patent/JP3483871B2/en not_active Expired - Lifetime
- 2001-02-15 AU AU2001232315A patent/AU2001232315A1/en not_active Abandoned
- 2001-02-15 CN CNB018016480A patent/CN1260269C/en not_active Expired - Lifetime
- 2001-02-15 KR KR10-2002-7001374A patent/KR100499718B1/en active IP Right Grant
- 2001-02-15 CN CNB2005100775650A patent/CN1322023C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5097004A (en) * | 1990-05-11 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Novel polyesters and their use in compostable products such as disposable diapers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020085869A (en) | 2002-11-16 |
| CN1260269C (en) | 2006-06-21 |
| KR100499718B1 (en) | 2005-07-07 |
| WO2001070848A1 (en) | 2001-09-27 |
| CN1702092A (en) | 2005-11-30 |
| CN1383437A (en) | 2002-12-04 |
| JP3483871B2 (en) | 2004-01-06 |
| AU2001232315A1 (en) | 2001-10-03 |
| TW550274B (en) | 2003-09-01 |
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